CZ2021464A3 - A method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent, recycling of the regenerating agent and the equipment for this - Google Patents

Abstract

The method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent and recycling of the regenerating agent consists in the fact that it contains the following steps: - purification of the raw contaminated liquid input in at least one multi-layered column containing carbon nanotubes - CNTs, immobilized on a carrier substrate for adsorption of impurities , possibly with coarse-grained inorganic and/or organic material as a composite mixture after achieving sorption of impurities, whereby the cleaned liquid is discharged outside the process; - subsequent regeneration of these carbon nanotubes - CNTs from adsorbed impurities in the same multi-layer column with a regeneration agent without removing the CNT tubes from the column and with subsequent recycling of the purified regeneration agent; and at the same time - switching the purification of the input raw polluted liquid to another at least one multi-layered column containing fresh, i.e. regenerated/new carbon nanotubes – CNTs to continue this continuous process. The solution further relates to a device for carrying out this method.

Description

A method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent, recycling of the regenerating agent and equipment for carrying out this method

Field of technology

The present invention generally relates to a complex method of cleaning a large spectrum of different liquids, especially water from various pollutants, especially for cases where it is necessary to clean a large amount of liquid, i.e. on a mass scale, with high efficiency and with minimal ecological burden and financial profitability. using adsorption/filtration nanomaterial.

Another object of the invention is also the regeneration of the polluted adsorbent from captured pollutants with subsequent recycling of the regenerate.

The invention further also includes a device for carrying out this method.

Current state of the art

There are many processes and materials for the purification of liquids and gases that have already been patented or described in the professional literature and that involve the adsorption/filtration nanomaterial, which are carbon nanotubes - CNT (carbon nanotubes). This is due to the fact that nanoparticles, which include CNTs, hold great promise for finding new technologies and materials and for improving industrial processes due to their unique properties.

Although more than 30 years have passed since the discovery of CNTs, there has still been no mass, industrial use of them in separation technologies, especially in the purification of water, organic liquids and gases, including air. This is due to the fact that it is difficult to immobilize CNTs so that they do not contaminate the purified fluid (liquid or gas). Many inventors have tried to address this shortcoming of CNTs.

The already filed Czech patent application CZ PV 2021-9 of the same applicant deals with the production of specially immobilized carbon nanotubes on a carrier substrate for the purification of liquids, especially water, where the described solution largely overcomes the mentioned problems, while the said application is incorporated here by reference in its entirety.

Until now known processes for adsorptive cleaning of liquids, especially water using CNTs for the sorption of contaminants according to the known state of the art, are not suitable for the mass scale of continuous cleaning of liquids, possibly only with unprofitable financial costs leading to the need to include additional equipment, or to use the properties of other interacting chemical substances and in addition to the increased demands on the workforce, also increase the environmental burden of the surroundings.

This is stated, for example, in patent application US 20150114819 A1, which solves the subsequent problem of CNT leakage into the environment by introducing a contaminated liquid into a pressure reactor and at high temperatures and pressures CNTs are oxidized to carbon dioxide. The disadvantage of this solution is the large additional investment expenses for the removal of CNT contamination and the high energy consumption, which makes this application uncompetitive in terms of mass deployment, e.g. for the treatment of drinking or waste water, where hundreds of cubic meters of water are processed per hour.

Another document, US 20150122735 A1, fixes CNTs to a cellulose ester membrane so that the CNTs are optimally perpendicular to the membrane surface and parallel to each other. This membrane production process has not yet been mastered industrially, and even the authors themselves state that their invention is

- 1 CZ 2021 - 464 A3 applicable only to cleaning small water sources such as tap water. The disadvantage of this invention is the impossibility of mass deployment.

Document US 20160251244 A1 describes the use of CNTs in the form of a membrane, where the CNTs are preferably doped with catalytic metals such as platinum to ensure chemical or electrochemical oxidation (ozone, O3) of micropollutants in drinking water. Although this invention is defined as innovative compared to existing oxidation technologies used in water treatment, its use is characterized by high production costs and high requirements for the qualification of service personnel. In addition, it does not solve the adsorption of oxidation products (polar organic substances such as aldehydes, ketones, carboxylic acids, which subsequently promote the renewal of microbial growth in the drinking water distribution network, which are also a potential health risk.

Patent US 7211320 B1 claims a composite material where CNTs are immobilized on an organic or ceramic substrate in the form of a membrane and at the same time CNTs modified by impregnation, functionalization, doping, charging, surface covering or irradiation are used. Such a process represents a high cost of membrane production, and in addition, the form of the membrane limits the amount of CNTs used in a given application, so for large-volume liquid purification applications, it is necessary to use a large number of expensive membranes, which forces the use of large-scale equipment and thus induces high investment costs. In addition, the adsorption capacity of these membranes is limited by the logically low content of CNTs.

Another example is patent KR 101490362 B1, where CNTs are injected together with a coagulant into a stream of purified water with subsequent CNT separation on a centrifuge. This process introduces additional chemicals into the treated water, is costly in terms of control accuracy and requires capital-intensive machinery (centrifuge). In addition, it is also energy-intensive.

Russian patent RU 2159743 C1 uses foam from an undefined polymer material to fix CNTs. Not all polymer materials can be used to treat, for example, drinking water, and in addition, they are a potential environmental burden when disposing of the filter. The material according to this invention, on the other hand, is based on completely recyclable materials.

Document US 2015166365 A1 indicates the advantage of CNTs impregnated with Fe nanoparticles for the removal of benzene from water. The material according to this invention advantageously uses the original catalytic iron particles to achieve an increased adsorption capacity for the removal of organic non-polar contaminations from water and thus excludes any pre-treatment of CNTs before further use.

Another document US 2015321168 A1 describes the immobilization of CNTs by coprecipitation of metal powders in an aqueous suspension of CNTs, where the CNTs are ultimately bound to precipitated metal particles in the form of horse tails, resulting in a composite material that can be removed from liquids, for example, by magnetic separation. One can well imagine the cost of this process and also the toxicological risks arising from the contact of purified water with powdered metals. In addition, part of the CNT is bound into precipitated particles and thus not completely accessible for pollutant adsorption.

The disadvantage of all the above-mentioned patent documents is either the need to modify the used CNTs in various ways or the need to immobilize them in the form of a membrane (there are hundreds of patents describing membranes with CNT content and it is not possible to cite them all here), or to use them in suspension, where removal by cytostatics is not ensured problematic CNTs from the produced liquid or use other materials as well. Most of the cited documents are practically unusable for the implementation of the present invention, due to the high production costs of the given material, significant requirements for additional investments and the need for qualified personnel.

To a certain extent, the utility model CZ 33685 U1 of the owner DEKONTA Slovensko spol. deals with a similar issue of water purification. s.r.o., introducing equipment designed for mass continuous purification of groundwater. The document describes several adsorption columns containing as sorption

- 2 CZ 2021 - 464 A3 material cartridges with polymer adsorbent, while the columns are used both for the sorption of organic contaminants from water and for the regeneration of the columns, where the captured impurities are decomposed.

In the mentioned solution, a polymeric adsorbent is used as an adsorption agent, specifically Amberlite resin of the XAD series, the disadvantage is that during regeneration the cartridge with the adsorbent must be removed from the column and moved to the distillation apparatus, where the regeneration of the adsorbent takes place at a relatively high temperature of 70 ^o C, with by the necessary security of all this additional operation, which at least increases economic costs and places high demands on the operation of the equipment.

The present invention aims to eliminate a large part of the above-mentioned disadvantages.

The essence of the invention

In its most general embodiment, the present invention provides a method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent and recycling of the regenerating agent, comprising the steps of:

- purification of the input raw polluted liquid in at least one multi-layer column containing for adsorption of impurities carbon nanotubes - CNTs, immobilized on a carrier substrate, possibly with coarse-grained inorganic and/or organic material as a composite mixture after the sorption of impurities has been achieved, while the purified liquid is removed outside the process;

- subsequent regeneration of these carbon nanotubes - CNTs from adsorbed impurities in the same multi-layer column with a regeneration agent without removing the CNT tubes from the column; and at the same time

- switching the purification of the input raw polluted liquid to another at least one multi-layer column containing fresh, i.e. regenerated/new carbon nanotubes - CNTs to continue this continuous method.

The subject of the present invention therefore relates to a method of complex, continuous, large-volume, adsorptive purification of liquids, especially for mass purification of drinking, utility and waste water (ART SAND Process technology), for example from organic liquids such as biofuels, preferably also from pesticides and drug residues using of adsorption/filtration nanomaterial, which are mainly immobilized carbon nanotubes - CNT, but it was found that granulated activated carbon can also be used as an adsorption material to a certain extent.

A significant advantage of the method of cleaning using this adsorbent - modified CNTs, mainly from the point of view of the economics of real operation, is its ability to be quickly regenerated without removing it from the adsorption apparatus. The fast kinetics of the adsorbent makes it possible to design small industrial devices with a small amount of adsorbent, for the regeneration of which a small amount of regeneration agent can be used. The kinetics of regeneration (desorption) is as fast as the kinetics of adsorption.

For this invention, the term "complex fluid purification" defines a method of purification from all basic groups of pollutants, which are pesticides, fungicides, herbicides, active medicinal ingredients, chlorinated hydrocarbons, but also bacteria and viruses.

The term: "purified fluid" in this invention means water, an organic liquid or a mixture of organic liquids, a gas, or a gas-air mixture; preferably water.

The basis of the fluid purification method according to the present invention are two adsorption columns, arranged in parallel or in series, one in the purification mode, the other in the regeneration mode from contaminants adsorbed on the absorbent from the purified liquid, the specific design of which was applied

- 3 CZ 2021 - 464 A3 by the applicant, utility model application PUV 2021 -39129, and which are filled with the above-mentioned mobilized CNT carbon nanotubes.

After switching to the first column containing fresh adsorptive material for continuous fluid purification, the contaminated nanotubes in the second column are continuously regenerated using an organic regeneration agent, which is subsequently recycled using reverse osmosis.

The present invention also includes an adsorbent material for cleaning said liquids in the said manner containing adsorbed impurities from the polluted liquid.

In addition to the cleaning method, the invention advantageously includes further steps of regeneration of the already used adsorbent with trapped impurities and subsequent recycling of the used regeneration agent after regeneration of the adsorbent.

At the same time, the invention also relates to a device for carrying out this method.

The essence of the invention is a method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent and recycling of the regenerating agent, while this method includes the following steps:

a) the raw, polluted input fluid is purified in the first multi-layer adsorption column containing carbon nanotubes immobilized on a carrier substrate for the adsorption of impurities, possibly with coarse-grained inorganic and/or organic material as a composite mixture, while the purified water is monitored by an analyzer and subsequently discharged outside the process;

b) after the measured adsorbed impurities, the first column is shut down and a second adsorption column with the same sorption material identical to the first adsorption column is included in the fluid purification system, which in the meantime undergoes cleaning from adsorbed impurities;

c) after its dewatering, the first column is washed with an organic regeneration agent, and the resulting regenerate is used for the subsequent regeneration of both columns after possible treatment; whereas

d) after completion of the regeneration of the first column according to step c), the excess amount of regenerating agent/regenerate is squeezed out using another medium, the column is rinsed with the washing liquid which is subsequently taken to the collection container for the diluted regenerate for further processing; and

e) the regenerated first column is subsequently shut down, and after exhausting the adsorbent with impurities in the second column, the first column is re-engaged for further continuous purification of the raw liquid and the second column is subjected to the same cleaning steps mentioned above.

Specific features of this method according to the invention are the steps:

a) the incoming raw polluted liquid, preferably water, is purified in the temperature range of 5 to 50 °C in the first multi-layer adsorption column (C1), containing for adsorption of impurities carbon nanotubes immobilized on a support substrate based on a fibrous natural or synthetic material in the form of a bulk bed, possibly with coarse-grained inorganic and/or organic material as a composite mixture, while the purified water is monitored by an analyzer and subsequently discharged outside the process;

b) after the increase of the values measured by the analyzer in the purified water to the set level, the adsorption column (C1) is shut down and the raw water is led to the second multi-stage adsorption column (C2) with fresh adsorbent for continuous operation, while the column (C1) with exhausted subjected to subsequent cleaning from adsorbed impurities with an adsorbent; and subsequently for

- 4 CZ 2021 - 464 A3

c) with the help of compressed gas - air, the adsorption column (C1) drains into the sewer, while its regeneration is subsequently carried out from the storage tank (RE2) with a regeneration agent based on a monohydric alcohol with a chain length of C1-C3, in an alkaline environment, and the regenerate after the first regeneration, after adjusting the pH/alcohol concentration, it is used again for further regeneration until the limit concentration of 25% by weight is reached. of substances captured in the regenerate, based on the weight of the regenerate; whereas

d) after the regeneration of the column (C1) according to step c) is completed, the excess amount of regeneration agent/regenerate is forced out with compressed gas into the storage tank (RE2), the column is flushed with a washing liquid, especially tap water or with organic and/or inorganic salts into the collection tank (RE1) for diluted regenerate for further processing; and

e) the regenerated column (C1) is subsequently shut down, and after the adsorbent has been exhausted by the impurities in the column (C2), the column (C1) is again included for further purification of the raw water.

According to the invention, an advantageous solution is that the cleaning method also includes step f), when regeneration and recycling of the regenerate, which includes:

after reaching the limit concentration of 25% wt. of the pollutants captured in the regenerate from step c), based on the weight of the regenerate, the regenerate is subsequently recycled, while the permeate from the recycling of the regenerate containing water and a monohydric alcohol, preferably with a chain length of C1-C3, in an alkaline environment is fed back to storage tank for the preparation of a fresh regeneration agent, while an even more advantageous solution according to the invention is that the regeneration agent from step c) or the permeate from step f) contains 15-40% by volume of ethanol, sodium ethanolate and/or alkali metal hydroxide with a concentration of 0 .01-5 mol/l in water.

A preferred regenerating agent for the adsorbent according to the present invention are aqueous solutions of low-molecular alcohols and their mixtures, such as methanol, ethanol or isopropanol, whose pH is adjusted with inorganic hydroxide to a value of 8-12, preferably 9-10. The concentration of low molecular weight alcohol or their mixtures is 20-90%, preferably 50-70%. The volume of the regeneration agent for complete regeneration of the adsorbent according to the invention corresponds to the volume of one adsorption bed.

Regeneration without removing it from the adsorption apparatus (i.e. in-situ) is economically very advantageous compared to the current state of the art, according to which during regeneration it is necessary to empty the adsorption column and take the adsorbent to the regeneration plant. Thereby, the adsorbent material according to the present invention saves the operator the cost of regeneration and reduces the carbon footprint of the operation.

According to a preferred solution of the method according to the present invention, the washing liquid from step d) of column regeneration containing about 4 vol.% ethanol is collected in a collecting tank, while about 80 vol.% pure water and the resulting concentrate containing about 20 vol% ethanol is returned to the storage tank as a regeneration agent.

The liquid purification method further preferably includes the recycling of the regenerate from step f), which is carried out using reverse osmosis, preferably at normal room temperature.

Yet another advantageous feature of the present invention is that the concentrate from step f) containing impurities is collected in a container outside the entire process for further processing.

According to the invention, the concentrate containing impurities from step f) is advantageously subjected to destruction by means of photocatalytic oxidation by UV radiation at a wavelength of 242 nm at room temperature, which is energetically, but especially ecologically very advantageous, since the destruction of pollutants is

- 5 CZ 2021 - 464 A3 do not use any chemical oxidizing agents at elevated temperatures, which is, for example, stated in the already mentioned CZ 33 685 U1.

Another object of the invention is the adsorbent itself, containing adsorbed impurities from a polluted liquid, especially water, which is at least one modification of carbon, especially carbon nanotubes immobilized on a carrier substrate or granular activated carbon, which has been subjected to cleaning and recycling using a regeneration agent.

Finally, yet another object of the present invention is in accordance with FIG. 1 device for adsorption large-volume purification of liquids, especially water, with cyclic regeneration of the adsorbent and recycling of the regenerating agent, while the device includes:

i. the main pump on the feed line of the purified liquid and at least two tiered adsorption columns with a parallel/series arrangement and pipeline connection on the one hand via the first inlet valve (V1) to the first tiered adsorption purification column (C1) and the outlet valve (V3) located behind the bottom of the column for draining the cleaned liquid, on the one hand through the second inlet valve (V2) to the second floor adsorption purification column (C2), and the outlet valve (V4) located behind the bottom of the column for draining the cleaned liquid, while on the common outlet pipe from the columns (C1, C2) an indicator of the absorbance of liquid impurities is arranged for switching the valves (V1, V2, V3, V4, V8 and V9) to the adsorption or regeneration mode of the tiered adsorption purification column C1 or C2;

ii. pipe (1) for the entry of pressure media - gas, washing water; to clean the adsorbed impurities on the adsorbent in the first or second floor adsorption cleaning column (C1) or (C2), opened in the direction of the fluid flow in front of the pipeline supplying the regeneration agent by means of valves (V6) and (V7) from the regeneration tank (RE2);

iii. at least one tank (RE2) with a regenerating agent connected by a pipe via a pump and an inlet valve (V6) on the one hand for the regeneration mod from naadsorb impurities to the first floor adsorption purification column (C1), on the other hand via an inlet valve (V7) for the regeneration mod from naadsorb impurities to second-stage adsorption purification columns (C2), while both the first-stage adsorption purification column (C1) and the second-stage adsorption purification column (C2) further contain a multi-purpose outlet valve (V8) from the first column that is opened in the upper half of the columns (C1, C2) (C1) or valve (V9) from the second column (C2) for draining the rinsing water, draining the adsorbent, draining the extruded regenerate or diluted regenerating agent using gas from the cleaned column (C1) or (C2) via the three-way valve (V5) back to tank (RE2) with regeneration agent;

while separate pipelines are further connected to the tank (RE2) with the regeneration agent through the valve (V10) and the valve (V11) for repeated physical recycling of the regeneration agent/recycled regenerate, while to the bottom of the tank (RE2) is connected through the valve (V14) a pipeline to recycling of regenerated adsorbent with discharge into collection tank (RE1); to the tank (RE2) with the regenerating agent, the recycled regenerating agent is pushed through the forward osmosis (FO) unit by the pump (P3) and the supply pipe from the sodium chloride reservoir to the forward osmosis is further connected to the pump (P6) to reduce the amount of water from the regenerating agent.

According to the invention, this device advantageously further comprises:

iv. at least one collection tank (RE1) containing a top-mouthed pipe for recycling the regenerate from the tank (RE2); further from the top with a connected pipe through a three-way valve (V5) for collecting the washing water with the diluted regeneration agent; while at the bottom of the collecting tank (RE1) there is an outlet pipe with a pump and a valve for forward osmosis and its connection to the tank (RE2) arranged in the direction of the regenerate flow.

- 6 CZ 2021 - 464 A3

According to the present invention, the said device further advantageously includes: a reverse osmosis unit with an arranged supply pipe from the collection tank (RE1) for recycling the regenerating agent by reverse osmosis, at the outlet of the unit connected by a pipe to the tank (RE2).

Clarification of drawings

Giant. 1 shows a schematic representation of a device according to the present invention.

Examples of implementation of the invention

Example 1

This example describes the method of water purification according to the present invention in the real operation of the technology called ART SAND Process when purifying drinking water from an underground well.

The adsorption column made of ALSI304 grade stainless steel with an outer diameter of 1.1 m, consisting of two adsorption layers, was filled with ART SAND adsorbent based on carbon nanotubes so that each layer of the adsorption column contained a layer of adsorbent 20 cm high. The column completed in this way had a total height of 1.5 m.

The column was equipped with a PVC device that diverted the water flowing from the individual floors of the adsorption column to one drain point. At the end of this part of the setup was a ball valve and recovery port. The inlet tube, which serves for supplying raw water to the adsorption column, is also equipped with a PVC device, which includes a pressure gauge, a ball valve and a regeneration port. Candle filters are placed in the pipe line leading to and from the column before and after the adsorption column. A fabric filter with a porosity of 1 pm is placed at the inlet of the column and at the outlet with a porosity of 0.1 pm.

The building in which the above-described adsorption column is located contained in the basement part a concrete storage concrete storage tank into which water spontaneously gushed concrete storage tank into which water spontaneously gushed from an underground well. The water accumulated in this tank was pumped by means of a self-priming pump through the inlet candle filter into the adsorption column of the ART SAND Process technology, where it passed through the adsorbent in all adsorption stages of the column. The water flowing out of the individual floors of the adsorption column was guided by a PVC device into one line of pipes, which further led it through the outlet candle filter back to the concrete sump in the basement part. The intake of water from the storage tank and the inflow of purified water from the ART SAND Process technology into the storage tank are located in the tank at the opposite ends of the imaginary diagonals connecting the two corners of this tank with a rectangular floor plan.

The ART SAND Process technology assembled according to the arrangement described above was operated for a long time at an average instantaneous water flow through the adsorption column of 1 l/s. The maximum instantaneous water flow through the column, for which the technology was designed, is 2 l/s. The retention time of the water in the column was 270 seconds.

During the operation of the technology at an average instantaneous water flow of 1 l/s, samples of raw water entering the adsorption column (IN) and water at the exit from the adsorption column (OUT) were taken. The concentrations of pesticide substances were determined in these water samples, which are summarized in Table 1. The data in the table show that after passing the water through the ART SAND Process technology, all present pesticide substances were eliminated.

- 7 CZ 2021 - 464 A3

Table 1: Analysis of water at the inlet (IN) and at the outlet (OUT) of the ART SAND Process technology.

Pointer Unit IN OUT COD Qty mg/l 3.64 2.97 acetochlor pg/l <0.02 <0.02 acetochlor ESA pg/l <0.03 <0.03 acetochlor OA pg/l <0.03 <0.03 alachlor pg/l <0.005 <0.005 alachlor ESA pg/l <0.03 <0.03 alachlor OA pg/l <0.03 <0.03 atrazine pg/l 0.045 <0.01 atrazine destehyl pg/l 0.128 <0.01 atrazine desisopropyl pg/l <0.01 <0.01 bentazon pg/l <0.01 <0.01 chloridazone pg/l <0.01 <0.01 chloridazone desphenyl (CHD) pg/l 0.058 <0.05 chloridazone methyl desphenyl pg/l <0.02 <0.02 chlortoluron pg/l <0.01 <0.01 clopyralid pg/l <0.025 <0.025 dimethachlor pg/l <0.01 <0.01 dimethachlor ESA pg/l <0.01 <0.01 dimethachlor OA pg/l <0.02 <0.02 hexazinone pg/l <0.01 <0.01 isoproturon pg/l <0.01 <0.01 metazachlor pg/l <0.01 <0.01 metazachlor ESA pg/l <0.03 <0.03 metazachlor OA pg/l <0.06 <0.06 tebuconazole pg/l <0.01 <0.01 terbuthylazine pg/l <0.01 <0.01 terbuthylazine desethyl pg/l <0.01 <0.01 terbuthylazine desethyl 2-hy pg/l <0.02 <0.02 metolachlor pg/l <0.01 <0.01 metolachlor ESA pg/l <0.03 <0.03 metolachlor OA pg/l <0.03 <0.03 atrazine 2-hydroxy pg/l <0.01 <0.01 pesticide l. total (relevant.) pg/l 0.173 0 sum (CHD+CHMD) pg/l 0.058 <0.05

Example 2

This example describes the operation of an adsorption column with a diameter of 22.5 cm of the ART SAND Process technology in the purification of drinking water from a subsurface source (well). The stainless steel adsorption column of the diameter described above was filled with ART SAND adsorbent material to a height of 20 cm and used during water purification during the production of non-alcoholic beverages. The residence time of the water 10 in the column was 120 seconds and the instantaneous average water flow was approximately 240 l/h. Adsorption columns were operated for 10 months in this location and under the parameters described above. The goal of installing the technology was the elimination of pesticide substances. The analysis of water entering the column (IN) and exiting the column (OUT) is summarized in Table 2.

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Table 2: Analysis of water at the inlet (IN) and at the outlet (OUT) performed according to the method of the present invention from the ART SAND Process technology.

Pointer Unit IN OUT Dicamba pg/l <0.025 <0.025 Clopyralid pg/l <0.025 <0.025 Acetochlor pg/l <0.020 <0.020 Acetochlor pg/l <0.030 <0.030 Acetochlor pg/l <0.030 <0.030 Alachlor pg/l <0.005 <0.005 Alachlor pg/l <0.030 <0.030 Alachlor pg/l <0.030 <0.030 Atrazine pg/l <0.010 <0.010 Atrazine desethyl pg/l <0.010 <0.010 Atrazine 2-hydroxy pg/l <0.010 <0.010 Bentazone pg/l <0.010 <0.010 Atrazine desethyl desisopropyl pg/l <0.020 <0.020 Dimethachlor pg/l <0.010 <0.010 Diuron pg/l <0.010 <0.010 Epoxyconazole pg/l <0.010 <0.010 Chloridazone pg/l <0.010 <0.010 Chlortoluron pg/l <0.010 <0.010 Isoproturon pg/l <0.010 <0.010 MCPA pg/l <0.020 <0.020 Metazachlor pg/l <0.010 <0.010 Metolachlor pg/l <0.010 <0.010 Metolachlor ESA pg/l <0.030 <0.030 Metolachlor OA pg/l <0.030 <0.030 Propiconazole pg/l <0.010 <0.010 Tebuconazole pg/l <0.010 <0.010 Terbuthylazine pg/l <0.010 <0.010 Terbuthylazine desethyl pg/l <0.010 <0.010 Terbuthylazine 2-hydroxy pg/l <0.010 <0.010 Metazachlor ESA pg/l <0.030 <0.030 Metazachlor OA pg/l <0.060 <0.060 Chloridazone desphenyl (CHD) pg/l 0.129 <0.050 Chloridazone methyl desphenyl (CHMD) pg/l 0.054 <0.020 Sum of CHD+CHMD pg/l 0.183 <0.050 Dimethachlor OA pg/l <0.020 <0.020 Dimethachlor ESA pg/l <0.010 <0.010 AMP pg/l <0.050 <0.050 Glyphosate pg/l <0.050 <0.050 Total pesticide substances (relevant) pg/l 0 0

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Example 3

According to the present invention, two adsorption columns of the ART SAND Process technology with a diameter of 22.5 cm (column K1 and K2) were connected in series in the elimination of pesticides and their metabolites from drinking water (underground well). The columns contained a total of approximately 5000 mL of ART SAND adsorbent (approximately 2500 mL each) and were operated continuously for 21 days at an average flow rate of 60 L/h. After saturation of the columns (after the detection of pesticide substances at the outlet of the second column in the series), the inflow of raw water into the columns was stopped and excess water was forced out of both columns using compressed gas, preferably compressed air. The dewatered adsorbent was thus prepared for regeneration.

The regenerating agent containing 15-40% by volume of ethanol and 60-85% by volume of water at pH 12.5 was forced by means of a pump at a defined speed first through the adsorbent in the AK2 column (second in order in the direction of the flow of purified water), from where it immediately flowed into columns AK1 (first in order in the direction of water flow). The regenerating agent was thus used for the simultaneous regeneration of two columns connected in series without the need to manipulate them.

Example 4

This example describes the recycling of ethanol from a regenerate that has reached the limit concentration of trapped substances when it is reused in the adsorbent regeneration procedure. The goal of the recycling procedure is to obtain the largest possible amount of ethanol from the regenerate and reuse it as an input raw material for the preparation of a new regeneration agent.

The composition of the regenerate obtained from the regeneration procedure was about 15-40 vol% ethanol and 60-85 vol% water. The total volume of the regenerate was 20 l and its pH was in the range of 9-10. At the same time, the regenerate contained organic substances that entered the regenerate by desorption from the surface of the saturated adsorbent during its regeneration.

The recycling of ethanol from the regenerate was carried out using a reverse osmosis unit, which contained specially designed membranes for this purpose. The reverse osmosis unit had an output of 150-200 l/h, a working pressure of up to 18 bar, an output of approx. 1.5 kW and an ethanol yield of approx. 90%. The regenerate was transported from the storage container by a pump under the necessary pressure and flow to the membranes in the osmotic unit. Here, permeate (purified ethanol solution without organic substances, 15-40% vol. ethanol, total volume 18 l) and concentrate (ethanol solution with concentrated organic substances, 20% vol. ethanol, total volume 2 l) were formed, which was gradually returned to the storage container with regenerate, where organic substances were concentrated. At the end of the recycling procedure, 18 l of recycled ethanol solution without organic substances and 2 l of concentrate, which contained all the organic substances originally present in the 20 l of regenerate, were created from 20 l of regenerated material.

The recycled ethanol solution (20% vol) obtained by the procedure described above was supplemented with a new ethanol solution (99.9% vol) so that the final ethanol concentration was 30% vol. This solution was finally alkalinized to pH 12 and reused at regeneration of saturated adsorbent.

The given examples of embodiments need to be taken into account only as illustrative of the invention, not as limiting the scope of protection of the invention, which is stated in the patent claims.

Claims (13)

1. A method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent and recycling of the regenerating agent, characterized by the fact that it contains the steps: - purification of the input raw polluted liquid in at least one multi-layer column containing for adsorption of impurities carbon nanotubes - CNTs, immobilized on a carrier substrate, possibly with coarse-grained inorganic and/or organic material as a composite mixture after the sorption of impurities has been achieved, while the purified liquid is removed outside the process; - the subsequent regeneration of these carbon nanotubes - CNTs from adsorbed impurities in the same multi-layer column with a regeneration agent without removing the CNT tubes from the column, and at the same time - switching the cleaning of the input raw polluted liquid to at least one more multi-layer column containing fresh, i.e. regenerated/new carbon nanotubes - CNT to continue this continuous method. 2. A method of complex, continuous, large-volume, adsorptive purification of liquids with cyclic regeneration of the adsorbent and recycling of the regenerating agent, according to claim 1, characterized in that it contains the steps: a) the raw, polluted input fluid is purified in the first multi-layer adsorption column containing carbon nanotubes immobilized on a carrier substrate for the adsorption of impurities, possibly with coarse-grained inorganic and/or organic material as a composite mixture, while the purified water is monitored by an analyzer and subsequently discharged outside the process; b) after the measured adsorbed impurities, the first column is shut down and a second adsorption column with the same sorption material identical to the first adsorption column is included in the water purification system, which in the meantime undergoes cleaning from adsorbed impurities; c) after its dewatering, the first column is washed with an organic regeneration agent, and the resulting regenerate is used for the subsequent regeneration of both columns after possible treatment; whereas d) after completion of the regeneration of the first column according to step c), the excess amount of regenerating agent/regenerate is squeezed out using another medium, the column is rinsed with the washing liquid which is subsequently taken to the collection container for the diluted regenerate for further processing; and e) the regenerated first column is subsequently shut down, and after exhausting the adsorbent with impurities in the second column, the first column is re-engaged for further continuous purification of the raw liquid and the second column is subjected to the same cleaning steps mentioned above. 3. The method according to claim 1 or 2, characterized in that it contains the steps: a) the incoming raw polluted liquid, in particular water, is purified in the temperature range of 5 to 50 ^o C in the first multi-layer adsorption column (C1), containing for adsorption of impurities carbon nanotubes immobilized on a carrier substrate based on fibrous natural or synthetic material in the form of a large-volume bed , possibly with coarse-grained inorganic and/or organic material as a composite mixture, whereby the purified water is monitored by an analyzer and subsequently discharged outside the process; b) after the increase of the values measured by the analyzer for the purified liquid, especially water, to the set level, the adsorption column (C1) is shut down and the raw liquid, especially water, is led to the second multi-stage adsorption column (C2) with fresh adsorbent for continuous operation, while the column (C1) with the exhausted adsorbent is subjected to subsequent cleaning from adsorbed impurities; and subsequently for c) with the help of compressed gas, the adsorption column (C1) drains into the sewer, while its regeneration is subsequently carried out from the storage tank (RE2) with a regenerating agent based on a monohydric alcohol with a chain length of C1-C3, in an alkaline environment, and the regeneration is carried out after the first regeneration, after adjusting the pH/alcohol concentration, it will be used again for further regeneration until the limit concentration of 25% by weight is reached. of substances captured in the regenerate, based on the weight of the regenerate; whereas d) after the regeneration of the column (C1) according to step c) is completed, the excess amount of regeneration agent/regenerate is forced out with compressed gas into the storage tank (RE2), the column is flushed with a washing liquid, especially tap water or with organic and/or inorganic salts into the collection tank (RE1) for diluted regenerate for further processing; and - 11 CZ 2021 - 464 A3 e) the regenerated column (C1) is subsequently shut down, and after the adsorbent has been exhausted by the impurities in the column (C2), the column (C1) is again included for further purification of the raw liquid. 4. The method according to claim 3, characterized in that it further comprises step f) of regeneration and recycling of the regenerate, which includes: f) after reaching the limit concentration of 25 wt.% of pollutants captured in the regenerate from step c), based on the weight of the regenerate, the regenerate is subsequently recycled, while the permeate from the recycling of the regenerate containing water and monohydric alcohol with a chain length of C1-C3, in an alkaline environment, is returned to the storage tank (RE2) to prepare fresh regeneration agent. 5. The method according to claim 3 or 4, characterized in that the regeneration agent from step c) a, respectively the permeate from step f) contains 15-40% by volume of ethanol, sodium ethanolate and/or alkali metal hydroxide with a concentration of 0.01 -5 mol/l in water. 6. A method according to any one of claims 3 to 5, characterized in that the washing liquid from step d) of column regeneration containing about 4% by volume of ethanol is collected in a collection tank (RE1), with the aid of forward osmosis and a drawing solution of 2M sodium chloride (NaCl) is removed from about 80% by volume of pure water and the resulting concentrate containing about 20% by volume of ethanol is returned to the storage tank (RE2) as a regeneration agent. 7. The method according to one of claims 4 to 6, characterized in that the recycling of the regenerate from step f) is carried out using reverse osmosis. 8. The method according to claim 3, characterized in that the concentrate from step f) containing impurities is collected in a container outside the entire process for further processing. 9. The method according to claim 8, characterized in that the concentrate containing impurities from step f) is subjected to destruction by means of photocatalytic oxidation by UV radiation at room temperature. 10. An adsorbent containing adsorbed impurities from a polluted liquid, especially water, subjected to cleaning and recycling according to one of the previous claims 4-7, characterized in that the adsorbent is at least one modification of carbon, in particular carbon nanotubes immobilized on a carrier substrate or granular activated carbon . 11. Equipment for adsorption large-volume cleaning of liquids, especially water, with cyclic regeneration of the adsorbent and recycling of the regenerating agent, characterized by the fact that it includes: i. the main pump on the feed line of the purified liquid and at least two tiered adsorption columns with a parallel/series arrangement and pipeline connection on the one hand via the first inlet valve (V1) to the first tiered adsorption purification column (C1) and the outlet valve (V3) located behind the bottom of the column for draining the cleaned liquid, on the one hand through the second inlet valve (V2) to the second floor adsorption purification column (C2), and the outlet valve (V4) located behind the bottom of the column for draining the cleaned liquid, while on the common outlet pipe from the columns (C1, C2) an indicator of the absorbance of liquid impurities is arranged for switching the valves (V1, V2, V3, V4, V8 and V9) to the adsorption or regeneration mode of the tiered adsorption purification column C1 or C2; ii. pipe (1) for the entry of pressure media - gas, washing water; to clean the adsorbed impurities on the adsorbent in the first or second floor adsorption cleaning column (C1) or (C2), opened in the direction of the fluid flow in front of the pipeline supplying the regeneration agent by means of valves (V6) and (V7) from the regeneration tank (RE2); iii. at least one tank (RE2) with a regenerating agent connected by a pipe via a pump and an inlet valve (V6) on the one hand for the regeneration mod from naadsorb impurities to the first floor adsorption purification column (C1), on the other hand via an inlet valve (V7) for the regeneration mod from naadsorb impurities to second-stage adsorption purification columns (C2), while both the first-stage adsorption purification column (C1) and the second-stage adsorption purification column (C2) further contain a multi-purpose outlet valve (V8) from the first column that is opened in the upper half of the columns (C1, C2) (C1), respectively the valve (V9) from the second column (C2) for draining the rinsing water, draining the adsorbent, draining the extruded regenerate or diluted regeneration agent using gas from the cleaned column (C1), - 12 CZ 2021 - 464 A3 or (C2), through the three-way valve (V5) back to the tank (RE2) with the regeneration agent; while separate pipelines are further connected to the tank (RE2) with the regeneration agent through the valve (V10) and the valve (V11) for repeated physical recycling of the regeneration agent/recycled regenerate, while to the bottom of the tank (RE2) is connected through the valve (V14) a pipeline to recycling of regenerated adsorbent with discharge into collection tank (RE1); to the tank (RE2) with the regenerating agent, the recycled regenerating agent is pushed through the forward osmosis (FO) unit by the pump (P3) and the supply pipe from the sodium chloride reservoir to the forward osmosis is further connected to the pump (P6) to reduce the amount of water from the regenerating agent. 12. The device according to claim 11, characterized in that it further contains: iv. at least one collection tank (RE1) containing a top-mouthed pipe for recycling the regenerate from the tank (RE2); further from the top with a pipe connected through a three-way valve (V5) for collecting the washing water with the diluted regeneration agent; while at the bottom of the collecting tank (RE1) there is an outlet pipe with a pump and a valve for forward osmosis and its connection to the tank (RE2) arranged in the direction of the regenerate flow. 13. The device according to claim 12, characterized in that it further includes: a reverse osmosis unit with an arranged supply pipe from the collection tank (RE1) for recycling the regenerating agent by reverse osmosis, at the outlet of the unit connected by a pipe to the tank (RE2).